WO2022043385A1 - Film à base de polypropylène - Google Patents

Film à base de polypropylène Download PDF

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Publication number
WO2022043385A1
WO2022043385A1 PCT/EP2021/073521 EP2021073521W WO2022043385A1 WO 2022043385 A1 WO2022043385 A1 WO 2022043385A1 EP 2021073521 W EP2021073521 W EP 2021073521W WO 2022043385 A1 WO2022043385 A1 WO 2022043385A1
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WO
WIPO (PCT)
Prior art keywords
film
random copolymer
methyl
polypropylene composition
mpa
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PCT/EP2021/073521
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English (en)
Inventor
Jingbo Wang
Markus Gahleitner
Klaus Bernreitner
Pauli Leskinen
Peter Niedersuess
Stefan Ortner
Original Assignee
Borealis Ag
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Application filed by Borealis Ag filed Critical Borealis Ag
Priority to BR112023002569A priority Critical patent/BR112023002569A2/pt
Priority to CN202180056270.2A priority patent/CN116134059A/zh
Priority to US18/020,680 priority patent/US20230257567A1/en
Publication of WO2022043385A1 publication Critical patent/WO2022043385A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene

Definitions

  • the present application relates to a film comprising a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units with a high tensile modulus in machine direction, a process for producing said film and the use of said polypropylene composition for the production of a film with a good balance of tensile modulus and protrusion impact.
  • Propylene copolymers are very well known and quite often used in the field of film making. In this technical area, polymers are required which combine high transparency, high mechanical strength and high impact strength. Quite often also high flowability of the used polymer is desired to reduce the process costs. However, it is demanding to fulfill all the required demands with one polymer since the improvement of one property is paid on the expense of another property.
  • WO 2014/187686 Al of Borealis AG discloses a polypropylene composition comprising a propylene random copolymer for unoriented film applications with good optical and mechanical properties.
  • the blown films of example section show good mechanical and impact properties but the optical properties leave something to be desired.
  • films showing such a good balance of properties can be prepared from polypropylene compositions comprising a random copolymer of propylene monomer units with ethylene comonomer units which has a rather low content of ethylene comonomer units of from 0.5 to 4.0 wt%, based on the total amount of monomer units in the random copolymer.
  • the present invention relates to a film, preferably an unoriented film, comprising a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units, wherein the random copolymer has a content of ethylene comonomer units of from 0.5 to 4.0 wt%, based on the total weight amount of monomer units in the random copolymer, the polypropylene composition has a melt flow rate MFR 2 of from 0.5 to 20.0 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, and the film has a tensile modulus in machine direction TM-MD in the range of from 450 to 850 MPa, when measured according to ISO 527-3 on a 50 pm monolayer cast film.
  • a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units, wherein the random copolymer has a content of
  • the present invention relates to a process for producing a film, preferably an unoriented film, as described above or below comprising the steps of a) Polymerizing the random copolymer of propylene monomer units and ethylene comonomer units in the presence of a single site catalyst system; b) Preparing the polypropylene composition; and c) Preparing the film.
  • the present invention relates to the use of a polypropylene composition
  • a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units, wherein the random copolymer has a content of ethylene comonomer units of from 0.5 to 4.0 wt%, based on the total weight amount of monomer units in the random copolymer, and the polypropylene composition has a melt flow rate MFR 2 of from 0.5 to 20.0 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, for the production of a film, preferably an unoriented film, with an improved balance of properties of tensile modulus and protrusion impact.
  • a propylene random copolymer is a copolymer of propylene monomer units and comonomer units - in the present case ethylene comonomer units - in which the comonomer units are distributed randomly over the polypropylene chain.
  • a propylene random copolymer includes a fraction, which is insoluble in xylene - xylene cold insoluble (XCI) fraction - in an amount of at least 70 wt%, more preferably of at least 80 wt%, still more preferably of at least 85 wt%, most preferably of at least 88 wt%, based on the total amount of propylene random copolymer. Accordingly, the propylene random copolymer does not contain an elastomeric polymer phase dispersed therein.
  • a propylene homopolymer is a polymer, which essentially consists of propylene monomer units. Due to impurities especially during commercial polymerization processes a propylene homopolymer can comprise up to 0.1 mol% comonomer units, preferably up to 0.05 mol% comonomer units and most preferably up to 0.01 mol% comonomer units.
  • Vis-breaking is a post reactor chemical process for modifying semi-crystalline polymers such as propylene polymers.
  • the propylene polymer backbone is degraded by means of peroxides, such as organic peroxides, via beta scission.
  • peroxides such as organic peroxides
  • beta scission The degradation is generally used for increasing the melt flow rate and narrowing the molecular weight distribution.
  • the present invention relates to a film comprising a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units, wherein the random copolymer has a content of ethylene comonomer units of from 0.5 to 4.0 wt%, based on the total weight amount of monomer units in the random copolymer, the polypropylene composition has a melt flow rate MFR 2 of from 0.5 to 20.0 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, and the film has a tensile modulus in machine direction TM-MD in the range of from 450 to 850 MPa, when measured according to ISO 527-3 on a 50 pm monolayer cast film.
  • the film of the present invention preferably is an unoriented film.
  • the random copolymer is a random copolymer with a molar majority of propylene monomer units and a molar minority of ethylene comonomer units.
  • the random copolymer in one embodiment can comprise further comonomer units selected from alpha-olefins having from 4 to 12 carbon atoms. It is, however, preferred that the random copolymer consists of propylene monomer units and ethylene comonomer units.
  • the random copolymer has a content of ethylene comonomer units of from 0.5 to 4.0 wt%, preferably from 0.7 to 3.5 wt%, more preferably from 1.0 to 3.0 wt% and most preferably from 1.3 to 2.8 wt%, based on the total weight amount of monomer units in the random copolymer.
  • the random copolymer preferably has a melt flow rate MFR 2 of from 0.5 to 20.0 g/10 min, more preferably from 1.0 to 15.0 g/10 min and most preferably from 1.5 to 12.5 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg.
  • the random copolymer preferably has a xylene cold solubles (XCS) content of from 0.05 to 5.00 wt%, more preferably from 0.10 to 3.50 wt% and most preferably from 0.20 to 2.50 wt%, based on the total weight content of the random copolymer.
  • XCS xylene cold solubles
  • the random copolymer preferably has a melting temperature Tm of from 122°C to 150°C, more preferably from 123°C to 148°C, still more preferably from 125°C to 144°C.
  • the random copolymer has been produced in the presence of a single site catalyst system, preferably comprising a metallocene catalyst.
  • the catalyst influences in particular the microstructure of the polymer.
  • polypropylenes prepared by using a metallocene catalyst provide a different microstructure compared to polypropylenes prepared by using Ziegler-Natta (ZN) catalysts.
  • ZN Ziegler-Natta
  • the most significant difference is the presence of regio-defects in metallocene-made polypropylenes. These regio-defects can be of three different types, namely 2,1-erythro (2, le), 2,1-threo (2, It) and 3,1 defects.
  • the term “2,1 regio defects” as used in the present invention defines the sum of 2,1 erythro regio-defects and 2,1 threo regio-defects. Accordingly it is preferred that the propylene copolymer (R-PP) according to this invention has a sum of 2,1- and 3,1 -regio-defects of at least 0.10 mol%, such as from 0.10 to 1.40 mol%, more preferably in the range of 0.20 to 1.20 mol%, still more preferably in the range of from 0.30 to 1.10 mol% and most preferably from 0.35 to 1.00 mol%, determined by 13 C-NMR spectroscopy.
  • the random copolymer is preferably produced in a sequential polymerization process in the presence of a single site catalyst system as defined below.
  • the term “sequential polymerization process” indicates that the random copolymer is produced in at least two reactors, preferably in two reactors, connected in series. Accordingly, the present process comprises at least a first reactor (Rl) and a second reactor (R2).
  • the term “polymerization reactor” shall indicate that the main polymerization takes place there. Thus in case the process consists of two polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • the term “consist of’ is only a closing formulation in view of the main polymerization reactors.
  • the first reactor (Rl) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry.
  • Bulk means a polymerization in a reaction medium that comprises of at least 60 wt% monomer.
  • the slurry reactor (SR) is preferably a (bulk) loop reactor (LR).
  • the second reactor (R2) is preferably a gas phase reactor (GPR).
  • GPR gas phase reactor
  • Such gas phase reactor (GPR) can be any mechanically mixed or fluid bed reactor.
  • the gas phase reactor (GPR) can be a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
  • the gas phase reactor is a fluidized bed type reactor, optionally with a mechanical stirrer.
  • the first reactor (Rl) is a slurry reactor (SR), like a loop reactor (LR), whereas the second reactor (R2) is a gas phase reactor (GPR).
  • a slurry reactor like a loop reactor (LR), and a gas phase reactor (GPR) are connected in series. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
  • SR slurry reactor
  • GPR gas phase reactor
  • the first random copolymer fraction of the random copolymer is produced, whereas in the second rector (R2) the second random copolymer fraction is produced.
  • the two random copolymer fractions can differ in their ethylene comonomer content or their molecular weight or both.
  • the random copolymer is a multimodal, preferably a bimodal, random copolymer.
  • the random copolymer fractions do not differ significantly in their ethylene comonomer content and their molecular weight.
  • the random copolymer is a unimodal random copolymer.
  • a preferred multistage process is a “loop-gas phase”-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the Spheripol® process of Basell described e.g. in figure 20 of the paper by Galli and Vecello, Prog.Polym.Sci. 26 (2001) 1287-1336.
  • the conditions for the first reactor (Rl), i.e. the slurry reactor (SR), like a loop reactor (LR), of step (a) may be as follows: the temperature is within the range of 40 °C to 110 °C, preferably between 60 °C and 100 °C, like 68 to 95 °C, the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar, hydrogen can be added for controlling the molar mass in a manner known per se.
  • the ethylene to propylene (C 2 /C 3 ) feed ratio is preferably in the range of from 10 to 50 mol/kmol.
  • the hydrogen to propylene (H 2 /C 3 ) feed ratio is adapted to achieve the desired molecular weight resp. melt flow rate.
  • the reaction mixture from step (a) (containing preferably the first random copolymer fraction) is transferred to the second reactor (R2), i.e. gas phase reactor (GPR), whereby the conditions are preferably as follows: the temperature is within the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C, the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to
  • the ethylene to propylene (C 2 /C 3 ) feed ratio is preferably in the range of from 50 to 120 mol/kmol.
  • the hydrogen to propylene (H 2 /C 3 ) feed ratio is adapted to achieve the desired molecular weight resp. melt flow rate.
  • the residence time can vary in the two reaction zones.
  • the residence time the first reactor (Rl), i.e. the slurry reactor (SR), like a loop reactor (LR), is in the range 0.2 to 4.0 hours, like 0.3 to 1.5 hours and the residence time in the gas phase reactor (GPR) will generally be 0.4 to 6.0 hours, like 0.5 to 4.0 hours.
  • the polymerization may be effected in a known manner under supercritical conditions in the first reactor (Rl), i.e. in the slurry reactor (SR), like in the loop reactor (LR), and/or as a condensed mode in the gas phase reactor (GPR).
  • the prepolymerization reaction is typically conducted at a temperature of 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.
  • the prepolymerization time is typically 0.1 to 1.0 hours, like 0.2 to 0.8 hours.
  • the random copolymer is preferably polymerized in the presence of a single-site catalyst system, more preferably of a metallocene catalyst complex and cocatalysts.
  • Preferred complexes of the metallocene catalyst include: rac-dimethylsilanediylbis[2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert- butylinden-1- yl] zirconium di chloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-l-yl][2-methyl-4- (4 ' -tertbutylphenyl)- 5-methoxy-6-tert-butylinden-l-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-l-yl][2-methyl-4- phenyl-5-methoxy-6-tert-butylinden-l-yl] zirconium di chloride, rac-anti-dimethyls
  • rac-anti-dimethylsilanediyl [2-methyl-4,8-bis-(3’,5’- dimethylphenyl)- 1 ,5,6,7-tetrahydro-s indacen- 1 -yl] [2-methyl-4-(3 ’,5 ’ - dimethylphenyl)-5-methoxy-6-tertl0butylinden-l-yl] zirconium dichloride.
  • a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst is used in combination with the above defined metallocene catalyst complex.
  • the aluminoxane cocatalyst can be one of formula (I): where n is from 6 to 20 and R has the meaning below.
  • Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula A1R 3 , A1R 2 Y and A1 2 R3Y 3 where R can be, for example, Cl- ClO-alkyl, preferably Cl-C5-alkyl, or C3-C10-cycloalkyl, C7-C12- arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or Cl-ClO-alkoxy, preferably methoxy or ethoxy.
  • the resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (I).
  • the preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content.
  • MAO methylaluminoxane
  • a boron containing cocatalyst can be used in combination with the aluminoxane cocatalyst.
  • the catalyst complex ideally comprises a co-catalyst, certain boron containing cocatalysts are preferred.
  • Especially preferred borates of use in the invention therefore comprise the trityl, i.e. triphenylcarbenium, ion.
  • Ph 3 CB(PhF 5 ) 4 and analogues therefore are especially favoured.
  • the catalyst system of the invention is used in supported form.
  • the particulate support material used is silica or a mixed oxide such as silica-alumina, in particular silica.
  • the use of a silica support is preferred. The skilled practitioner is aware of the procedures required to support a metallocene catalyst.
  • the catalyst system corresponds to the ICS3 of PCT/EP2020/064194.
  • the polypropylene composition comprises the random copolymer as described above or below.
  • the random copolymer is present in the polypropylene composition in an amount of at least 90.00 wt%, such as from 90.00 wt% to 100 wt%, more preferably from 92.50 wt% to 99.99 wt% and most preferably from 95.0 wt% to 99.90 wt%.
  • the polypropylene composition can comprise further polymer(s) in addition to the random copolymer, such as propylene based polymers, like propylene homopolymers or propylene random copolymers. If present, the amount of further polymer(s) is preferably less than 10.0 wt%, preferably not more than 5.0 wt%. It is, however, preferred that the random copolymer is the only polymer in the polypropylene composition.
  • the polypropylene composition usually comprises additives suitable for film applications. Suitable additives are e.g. antioxidants, slip agents and antiblocking agents. Preferably, the additive content is from 0.01 to 5.00 wt%, more preferably from 0.10 to 1.00 wt%, based on the total weight content of the polypropylene composition.
  • the polypropylene composition can comprise an alphanucleating agent.
  • the alpha-nucleating agent is preferably selected from the group consisting of
  • salts of monocarboxylic acids and polycarboxylic acids e.g. sodium benzoate or aluminum tert-butylbenzoate, and
  • dibenzylidenesorbitol e.g. 1,3 : 2,4 dibenzylidenesorbitol
  • Cx-C 8 -alkyl- substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as l,2,3-trideoxy-4,6:5,7-bis-O-[(4- propylphenyl)methylene]-nonitol, and
  • salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4,6-di-tert- butylphenyl) phosphate or aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di- t-butylphenyl)phosphate], and
  • the polypropylene composition contains from 0.00001 to 5.00 wt%, more preferably from 0.0001 to 2.50 wt% of the alpha-nucleating agent.
  • the amount of pure alpha-nucleating agent in the polypropylene composition (without optional carrier polymer of a master batch) is preferably in the range of from 0.01 to 2000 ppm, more preferably from 0.1 to 1000 ppm.
  • the alpha-nucleating agent is preferably selected from the group consisting of dibenzylidenesorbitol (e.g. 1,3 : 2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as 1,2,3- trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • dibenzylidenesorbitol e.g. 1,3 : 2,4 dibenzylidene sorbitol
  • dibenzylidenesorbitol derivative preferably dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di
  • vinylcycloalkane polymers such as e.g. vinylcyclohexane (VCH) polymers.
  • VCH vinylcyclohexane
  • BNT Borealis Nucleation Technology
  • the additives and the alpha-nucleating agent can be added to the polypropylene composition as an isolated raw material or in a mixture with a carrier polymer, i.e. in a so-called master batch.
  • the amount of the carrier polymer of the master batch thereby is calculated to the amount of the additives or the alpha-nucleating agent.
  • the additives and alpha-nucleating agents are generally commercially available and are described, for example, in "Plastic Additives Handbook", 6th edition, 2009 of Hans Zweifel (p. 967 - 983).
  • the polypropylene composition has a melt flow rate of 0.5 to 20.0 g/10 min, more preferably from 1.0 to 15.0 g/10 min and most preferably from 1.5 to 12.5 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg.
  • the melt flow rate of the polypropylene composition mainly depends on the melt flow rate of the random copolymer.
  • the random copolymer has a rather low melt flow rate of less than 5.0 g/lOmin or even less than 3.5 g/lOmin.
  • the melt flow rate of the polypropylene composition can be increased by vis-breaking in the presence of a peroxide, such as an organic peroxide, preferably during the compounding step in which the optional additives and alphanucleating agent are added to the polypropylene composition.
  • the peroxide is then usually selected depending on the compounding conditions. Suitable peroxides are commercially available and disclose optimum visbreaking conditions such as temperature, pressure, operation time and amount in their technical data sheets.
  • the polypropylene composition After vis-breaking, the polypropylene composition usually has a melt flow rate of from 5.5 to 20.0 g/10 min, preferably from 6.0 to 17.5 g/10 min, more preferably from 6.5 to 15.0 g/10 min and most preferably from 7.0 to 13.0 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg.
  • the polypropylene composition preferably has a melting temperature Tm of from 122°C to 150°C, more preferably from 123°C to 148°C, still more preferably from 125°C to 144°C.
  • the polypropylene composition preferably has a crystallization temperature Tc of from 90°C to less than 115°C, more preferably from 95°C to 113°C, still more preferably from 98°C to 110°C.
  • the present invention is related to a film, preferably an unoriented film, comprising the polypropylene composition as described above or below.
  • film preferably relates to an unoriented film.
  • the film preferably comprises at least 70 wt%, preferably comprising at least 80 wt%, more preferably comprising at least 90 wt%, still more preferably comprising at least 95 wt%, yet more preferably comprising at least 99 wt%, of the instant polypropylene composition.
  • the film consists of the instant polypropylene composition.
  • the film is a cast film, a roll-stack film or a blown film, like an air cooled blown film. More preferably, the film is a cast film or a roll-stack film. Even more preferably, the film is a cast film.
  • the film according to this invention is preferably not a biaxially oriented film.
  • the film according to the instant invention is a cast film or blown film.
  • the film has a thickness of 5 to 2,000 pm, preferably of 10 to 1,000 pm, more preferably of 15 to 700 pm, like of 20 to 500 pm.
  • the film according to the present invention surprisingly has a good balance of properties as regards mechanical properties, impact properties, optical properties and other film properties. Thereby, it has been found that by adding an alpha nucleating agent some film properties such as coefficient of friction (CoF) and hot tack force can be further improved where needed without sacrificing the other properties.
  • CoF coefficient of friction
  • the film has a tensile modulus in machine direction TM-MD in the range of from 450 to 850 MPa, preferably in the range of from 470 to 800 MPa and most preferably in the range of from 500 to 750 MPa, when measured according to ISO 527-3 on a 50 pm monolayer cast film.
  • the film further preferably has a tensile modulus in transverse direction TM-TD in the range of from 450 to 850 MPa, preferably in the range of from 470 to 800 MPa and most preferably in the range of from 500 to 750 MPa, when measured according to ISO 527-3 on a 50 pm monolayer cast film.
  • the film preferably has a protrusion impact of from 30.0 to 125.0 N, more preferably of from 32.5 to 110. O N, most preferably from 35.0 to 100.0 N, when measured according to ASTM D5748 on a 50 pm monolayer cast film.
  • the film preferably has a haze of from 0 to 2.5%, more preferably from 0 to 2.4%, most preferably from 0 to 2.3%, when measured according to ASTM D 1003 on a 50 pm monolayer cast film.
  • the film has a sealing initiation temperature SIT of from 105 to 120°C, more preferably from 107 to 118°C, most preferably from 109 to 116°C, when measured on a 50 pm monolayer cast film.
  • the film preferably has a coefficient of friction at 7 days CoF@7days of from 0.01 to 0.30, more preferably from 0.02 to 0.27, most preferably 0.03 to 0.25, when measured according to DIN 53 375 on a 50 pm monolayer cast film.
  • the film preferably has a hot tack force HTF of from 1.5 to 5.0 N, more preferably from 2.0 to 4.0 N, most preferably from 2.5 to 3.5 N, when measured according to ASTM F 1921 - 98 (2004), method B on a 50 pm monolayer cast film.
  • the coefficient of friction and hot tack force are preferably at the upper end of the ranges described above for films comprising an alpha-nucleated polypropylene composition.
  • the present invention relates to a process for producing a film as described above or below comprising the steps of a) Polymerizing the random copolymer of propylene monomer units and ethylene comonomer units in the presence of a single site catalyst system; b) Preparing the polypropylene composition; and c) Preparing the film.
  • the film is preferably an unoriented film prepared by cast film or blown film extrusion.
  • the film preferably being an unoriented film
  • the polypropylene composition and the random copolymer are preferably defined as described in any embodiments above or below.
  • the random copolymer is preferably polymerized as described above or below.
  • the polypropylene composition is preferably prepared in a compounding step optionally by adding the additives, the alpha-nucleating agent and the additional polymers as described above or below, preferably optionally the additives and the alpha-nucleating agent, during the compounding step.
  • additives and the alpha-nucleating agent are added.
  • the polypropylene composition is subjected to a visbreaking step, preferably during the instant compounding step after polymerization, as described above or below.
  • the compounding can be conducted in any suitable extruder using conventional compounding conditions.
  • suitable extruders typically used are co-rotating twin-screw extruders including special mixing sections operated in the temperature range from 180 to 280°C.
  • the film is preferably prepared by introducing the polypropylene composition into a suitable film line.
  • the polypropylene composition is extruded through a slot extrusion die onto a chill roll to cool the polymer to a solid film.
  • the polypropylene composition is firstly compressed and liquefied in an extruder, it being possible for any additives to be already added to the polymer or introduced at this stage via a masterbatch.
  • the melt is then forced through a flat-film die (slot die), and the extruded film is taken off on one or more take-off rolls, during which it cools and solidifies. It has proven particularly favorable to keep the take-off roll or rolls, by means of which the extruded film is cooled and solidified, at a temperature from 10 to 50°C, preferably from 15 to 40°C.
  • the polypropylene composition melt is extruded through an annular die and blown into a tubular film by forming a bubble which is collapsed between nip rollers after solidification.
  • the blown extrusion can be preferably effected at a temperature in the range 160 to 240 °C, and cooled by water or preferably by blowing gas (generally air) at a temperature of 10 to 50 °C to provide a frost line height of 0.5 to 8 times the diameter of the die.
  • the blow up ratio should generally be in the range of from 1.5 to 4, such as from 2 to 4, preferably 2.5 to 3.5.
  • the resulting film preferably shows all properties as described above or below.
  • the present invention relates to the use of a polypropylene composition
  • a polypropylene composition comprising a random copolymer of propylene monomer units and ethylene comonomer units, wherein the random copolymer has a content of ethylene comonomer units of from 0.5 to 4.0 wt%, based on the total weight amount of monomer units in the random copolymer, and the polypropylene composition has a melt flow rate MFR 2 of from 0.5 to 20.0 g/10 min, determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, for the production of a film, preferably an unoriented film, with an improved balance of properties of tensile modulus and protrusion impact.
  • the film preferably the unoriented film, the polypropylene composition and the random copolymer are defined as described in any embodiments above or below.
  • the resulting film preferably shows all properties as described above or below.
  • MFR 2 (230 °C) is measured according to ISO 1133 (230°C, 2.16 kg load).
  • the MFR 2 of the polypropylene composition is determined on the granules of the material, while the MFR 2 of the melt-blown web is determined on cut pieces of a compression-molded plaque prepared from the web in a heated press at a temperature of not more than 200°C, said pieces having a dimension which is comparable to the granule dimension.
  • the xylene soluble fraction at room temperature (xylene cold soluble XCS, wt%): The amount of the polymer soluble in xylene is determined at 25 °C according to ISO 16152; 5 th edition; 2005-07-01.
  • NMR nuclear-magnetic resonance
  • the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification.
  • Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ 16 decoupling scheme ⁇ zhou07,busico07 ⁇ .
  • a total of 6144 (6k) transients were acquired per spectra.
  • Quantitative ⁇ CQH ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present.
  • the comonomer fraction was quantified using the method of Wang et. al. ⁇ wangOO ⁇ through integration of multiple signals across the whole spectral region in the ⁇ CQH ⁇ spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
  • Characteristic signals corresponding to regio defects were observed ⁇ resconiOO, wangOO ⁇ .
  • the presence of isolated 2,1-erythro regio defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.
  • the presence of 2,1 regio defect adjacent an ethylene unit was indicated by the two inequivalent SaP signals at 34.9 ppm and 34.7 ppm respectively and the Tyy at 34.1 ppm.
  • the amount of 2,1 regio defect adjacent to ethylene (PE21) was quantified using the methine site at 34.1 ppm (I Try ):
  • the total amount of propene (P to tai) was quantified based on the methyl region (ICJB) between 23.0 and 19.9 ppm with correction undertaken for sites included in this region not related to propene insertion.
  • the methyl group P yy resulting from 2, 1 regio defect adjacent to ethylene is already present in I CH 3: Ptotai — IcH3 + 2 * P21e isolated
  • the isolated 2,1-erythro regio defects (P 2ie isolated) is multiplied by 2 to take into account the two (2) propene units in the 2, 1-erythro regio defects.
  • the total amount of 2,1 defects was quantified as following:
  • Tensile modulus in machine and transverse direction were determined according to ISO 527-3 at 23°C on monolayer cast films with a thickness of 50 pm produced as indicated below. Testing was performed at a cross head speed of 1 mm/min.
  • Protrusion impact was determined according to according to ASTM D5748 on monolayer cast films with a thickness of 50 pm produced as indicated below.
  • Transparency, haze and clarity were determined according to ASTM D1003-00 on monolayer cast films with a thickness of 50 pm produced as indicated below.
  • the method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or cast films.
  • the sealing temperature range is the temperature range, in which the films can be sealed according to conditions given below.
  • the lower limit heat sealing initiation temperature (SIT)
  • SIT heat sealing initiation temperature
  • SET breaking end temperature
  • Specimen is sealed A to A at each sealbar temperature and seal strength (force) is determined at each step. The temperature is determined at which the seal strength reaches 3 N. Hot tack force:
  • the hot-tack force was determined according to ASTM Fl 921-12 - Method B on a J&B Hot-Tack Tester on monolayer cast films with a thickness of 50 gm produced as indicated below.
  • the minimum conditioning time of test specimen in standard atmosphere before start testing is at least 16 h.
  • the minimum storage time between extrusion of film sample and start testing is at least 88 h.
  • the hot tack measurement determines the strength of heat seals formed in the films, immediately after the seal has been made and before it cools to ambient temperature.
  • the hot-tack measurement was performed under the following conditions.
  • the hot tack force was measured as a function of temperature within the temperature range and with temperature increments as indicated above.
  • the number of test specimens were at least 3 specimens per temperature.
  • the output of this method is a hot tack curve; a force vs. temperature curve.
  • the hot tack force (HTF) is evaluated from the curve as the highest force (maximum peak value) with failure mode "peel".
  • Coefficient of friction (CoF) (including static CoF and dynamic CoF) as a measure of the frictional behavior of the film is determined using a method according to ISO 8295:1995 and ASTM D1894: 2008 on monolayer cast films with a thickness of 50 pm produced as indicated below.
  • the single site catalyst system used for the polymerization of the random copolymers RC1, RC2, RC3 and RC4 (according to the invention) is prepared as follows:
  • the catalyst used was 74w/z-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)- l,5,6,7-tetrahydro-s-indacen-l-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6- /czV-butylinden- l -yl] zirconium di chloride as disclosed in PCT/EP2020/064194as ICS3.
  • a steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20 °C.
  • silica grade DM-L-303 from AGC Si-Tech Co pre-calcined at 600 °C (5.0 kg) was added from a feeding drum followed by careful pressurising and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min.
  • 30 wt.-% solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90°C and stirred at 90 °C for additional two hours.
  • the polymerization for preparing the random copolymers of propylene with ethylene comonomer units RC1, RC2, RC3 and RC4 (all according to the invention) as well as random copolymer (comparative) were performed in a Borstar pilot plant with a 2- reactor set-up (loop - gas phase reactor (GPR 1)) preceded by a prepolymerization reactor.
  • GPR 1 loop - gas phase reactor
  • RC1 to RC4 were polymerized in the presence of the single site catalyst (SSC) system as described above, whereas RC5 was polymerized in the presence of the phthalate- free Ziegler-Natta (ZN) catalyst as described above.
  • SSC single site catalyst
  • ZN phthalate- free Ziegler-Natta
  • Table 1 the polymerization conditions and properties for RC1, RC2, RC3 and RC4 are given.
  • Table 1 Polymerization conditions and of the random copolymers RC1 to RC5 4. Preparation of the compositions and films of examples IE1-IE4 and CE1- CE2
  • melt flow rates of the random copolymers RC1-RC3 and RC5 were modified by vis-breaking during a compounding step in a twin extruder. During said compounding step additives as described below were added.
  • Random copolymer RC1 was visbroken to a final melt flow rate MFR 2 of 8.0 g/10 min to obtain the polypropylene composition of inventive example IE1.
  • Random copolymer RC2 was visbroken to a final melt flow rate MFR 2 of 12.0 g/10 min to obtain the polypropylene composition of inventive example IE2.
  • Random copolymer RC2 was also visbroken to a final melt flow rate MFR 2 of 7.5 g/10 min to obtain the polypropylene composition of inventive example IE3.
  • Random copolymer RC3 was visbroken to a final melt flow rate MFR 2 of 12.0 g/10 min to obtain the polypropylene composition of inventive example IE4.
  • Random copolymer RC5 was visbroken to a final melt flow rate MFR 2 of 8.0 g/10 min to obtain the polypropylene composition of comparative example CE1.
  • Random copolymer RC5 was separately also visbroken to a final melt flow rate MFR 2 of 11.0 g/10 min to obtain the polypropylene composition of comparative example CE2.
  • Irganox B215 a l:2-mixture of Pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4-hydroxyphenyl)-propionate, CAS-no. 6683-19-8, and Tris (2,4-di-t-butylphenyl) phosphite, CAS-no. 31570-04-4, commercially available from BASF SE, Germany
  • 150 ppm magnesium oxide CAS-no. 1309-48-4
  • the polypropylene compositions were extruded to monolayer cast films with a thickness of 50 pm using a cast film co-extrusion line.
  • compositions and films are listed in Table 2 below.
  • Table 2 Properties of the compositions and cast films of IE1-IE3 and CE1
  • inventive examples IE1 to IE3 all show improved mechanical properties in tensile modulus and improved impact properties in protrusion impact at comparable optical properties in haze when compared to comparative example CE1.
  • Crodamide OR oleamide, CAS-no. 301-02-0, commercially available from Croda Polymer Additives, UK
  • 2000 ppm Gasil AB 725 silicon dioxide, CAS-no. 7631-86-9, commercially available from PQ Corporation, UK
  • 1000 ppm calcium stearate CAS-no. 1592-23-0
  • 2000 ppm Irganox B215 a l :2-mixture of Pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4- hydroxyphenyl)-propionate, CAS-no.
  • Tris (2,4-di-t-butylphenyl) phosphite, CAS-no. 31570-04-4, commercially available from BASF SE, Germany) were added during the compounding step.
  • the polypropylene compositions were extruded to monolayer cast films with a thickness of 50 pm using a Collin pilot-scale cast film line.
  • compositions and films are listed in Table 3 below.
  • Table 3 Properties of the compositions and cast films of IE4 and CE2
  • inventive example IE4 also shows improved mechanical properties in tensile modulus and improved impact properties in protrusion impact at comparable optical properties in haze when compared to comparative example CE1. Additionally IE1 shows improved sealing properties in lower SIT.
  • the random copolymer RC4 was compounded in a twin extruder. Due to its high MFR 2 visbreaking was not necessary. During said compounding step additives as described below were added.
  • Irganox 1010 Pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4-hydroxyphenyl)-propionate, CAS-no. 6683-19-8) and 600 ppm Irgafos 168 (Tris (2,4-di-t-butylphenyl) phosphite, CAS-no. 31570-04-4, both commercially available from BASF SE, Germany), 2000 ppm Crodamide OR (oleamide, CAS-no.
  • IE6 additionally 2.0 wt% HF995MO, being a highly crystalline propylene homopolymer produced by Borealis Nucleation Technology (BNT), (commercially available from Borealis AG) as alpha-nucleation masterbatch, comprising poly(vinyl cyclohexane) and 0.7 wt% of talc were added during the compounding step to produce an alpha-nucleated polypropylene composition.
  • BNT Borealis Nucleation Technology
  • compositions and films are listed in Table 4 below.
  • alpha nucleation has no effect on the mechanical and impact properties and the SIT of the film but improves the optical properties, the hot tack force and the migration of slip is faster. In addition, the hot-tack force HTF is improved.

Abstract

La présente invention concerne un film, de préférence un film non orienté, comprenant une composition de polypropylène comprenant un copolymère aléatoire de motifs monomères de propylène et de motifs comonomères d'éthylène, le copolymère aléatoire présentant une teneur en motifs comonomères d'éthylène de 0,5 à 4,0 % en poids, sur la base de la quantité de poids total des motifs monomères dans le copolymère aléatoire. La composition de polypropylène présente un indice de fluidité à chaud MFR2 de 0,5 à 20,0 g/10 min, déterminé selon la norme ISO 1133 à une température de 230°C et sous une charge de 2,16 kg. Le film présente un module de traction dans la direction machine TM-MD dans la plage de 450 à 850 MPa, lorsqu'il est mesuré selon la norme ISO 527-3 sur un film coulé monocouche de 50 µm. L'invention concerne également un procédé de production d'un tel film et l'utilisation d'une telle composition de polypropylène pour la production d'un film présentant un équilibre amélioré de propriétés de module de traction et d'impact de saillie.
PCT/EP2021/073521 2020-08-27 2021-08-25 Film à base de polypropylène WO2022043385A1 (fr)

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US18/020,680 US20230257567A1 (en) 2020-08-27 2021-08-25 Polypropylene based film

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WO2023062010A1 (fr) 2021-10-14 2023-04-20 Borealis Ag Copolymère statistique de propylène-éthylène avec distribution d'éthylène hautement randomisée

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EP4253453A1 (fr) * 2022-04-01 2023-10-04 Borealis AG Film soufflé
WO2023208875A1 (fr) * 2022-04-26 2023-11-02 Borealis Ag Procédé de recyclage de films de polypropylène
WO2024013126A1 (fr) * 2022-07-11 2024-01-18 Borealis Ag Procédé de préparation de copolymères aléatoires de propylène-éthylène pour applications dans des tuyaux
WO2024013128A1 (fr) * 2022-07-11 2024-01-18 Borealis Ag Copolymère aléatoire de propylène-éthylène pour des applications de tuyau

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